US2449163A - Process for the preparation of alpha, alpha-dialkyl beta-chloropropionic acids - Google Patents
Process for the preparation of alpha, alpha-dialkyl beta-chloropropionic acids Download PDFInfo
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- US2449163A US2449163A US687961A US68796146A US2449163A US 2449163 A US2449163 A US 2449163A US 687961 A US687961 A US 687961A US 68796146 A US68796146 A US 68796146A US 2449163 A US2449163 A US 2449163A
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- carbon monoxide
- acids
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- 238000000034 method Methods 0.000 title description 18
- 238000002360 preparation method Methods 0.000 title description 11
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical class OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 title 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 description 15
- 239000002253 acid Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- -1 olefin hydrocarbon Chemical class 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- YBJGQSNSAWZZHL-UHFFFAOYSA-N 3-chloro-2,2-dimethylpropanoic acid Chemical compound ClCC(C)(C)C(O)=O YBJGQSNSAWZZHL-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- USEGQJLHQSTGHW-UHFFFAOYSA-N 3-bromo-2-methylprop-1-ene Chemical compound CC(=C)CBr USEGQJLHQSTGHW-UHFFFAOYSA-N 0.000 description 1
- HVSJHYFLAANPJS-UHFFFAOYSA-N 3-iodo-2-methylprop-1-ene Chemical compound CC(=C)CI HVSJHYFLAANPJS-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 102100027835 Cell death regulator Aven Human genes 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000256257 Heliothis Species 0.000 description 1
- 101000698131 Homo sapiens Cell death regulator Aven Proteins 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- MJCYPBSRKLJZTB-UHFFFAOYSA-N trifluoroborane;dihydrate Chemical compound O.O.FB(F)F MJCYPBSRKLJZTB-UHFFFAOYSA-N 0.000 description 1
- MVJKXJPDBTXECY-UHFFFAOYSA-N trifluoroborane;hydrate Chemical class O.FB(F)F MVJKXJPDBTXECY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
Definitions
- This invention relates to. a process. for the proauction of alpha,a1pha-disubstituted-beta-halogenop'ropioni'c acids and, more particularly, of alphaalpha-dirnethyhbeta-chloropropionic acid.
- U. S. Patent 1,924,762 a process is disclosed for the preparation of carboxylic acids by reacting an olefin hydrocarbon with carbon. monoxide and steam, desirably with an inorganic acid, over certain catalysts.
- This. invention has as an object the preparation of monomeric halogenated carboxylicacids.
- Example I A silver-lined, high-pressure reactor equipped 100 C. with a resultant pressure. rise to 570 atm. With the temperature maintained at 100-102 C. throughout the reaction, methallyl chloride was then injected at about 40 parts per hour over a period of 1.5 hours. The total amount of meth-- allyl chloride. so injected was about 59 parts by weight. By this time, the pressure had reached 750 atm. During the next two hours in which the reaction was continued without further addition of methallyl chloride the pressure dropped to 720 atm. where it remained constant for the next 6.5 hours, indicating that the reaction required at most 3.5 hours, although the totalreaction? time used amounted to approximately ten hours. The reactor was cooled to 25'. C., excess carbon monoxide was bled oil, and the liquid reaction products were discharged, diluted with water and steam distilled. The residue contained a dark oil amounting to 4.5 parts. The
- This fraction had a very valent hydrocarbon radicals sharp freezing point of 44, C.
- the neutral The ethylemc compounds ractedfby the prom equivalent was found to be 137.0 as compared to ess i v nt f't mul Calculatfid value Of C5H9O2C1 Of 4.5
- the process of this invention is operable only 3 with olefinic compoundswherein the R!- attached gag to the ethylenic carbon bearing the -CH2X X" ⁇ Omx group ishydrocarbon since those olefinic com- I pounds having hydrogen on the carbon bearing wherein X is ha1ogen, 'i. e.,.
- X is a halogen
- R is hydrogen or a monovalent hydrocarbon radical of 1 to 6 carbon atoms, preferably phenyl or alkyl
- R is a monovalent hydrocarbon radical of 1 to 6 carbon atoms, preferably phenyl or alkyl.
- X is chlorine or bromine, i. e., a halogen from the 2d to 3d periods of the periodic system are preferred because these are the most readily available and economical to use.
- Specific examples include 3-bromo-2-methylpropene, 3-iodo-2-methylpropene, 1-chloro-2- methy1-2-butene, 1-bro-mo-2-methyl-2-butene, 1- bromo-2,6-dimethyl-2-heptene, and l-bromo- 2,3-diphenyl-2-butene.
- the molar ratio of the ethylenic compounds of this invention to the carbon monoxide may vary within the range of from 1:1 to 1:20 or more. In general. however, it is preferable to use a large excess of carbon monoxide and molar ratios of 1:5 to 1:10 have been found to be especially desirable.
- Strong acid catalysts in general, are suitable for the operation of this invention although the acid-reacting hydrates, for example, such as BF3.(H20)r, I-I2SO4.(H20) :c, and H3PO4.(I-I20)e and the like are especially desirable.
- the subscript a: in the foregoing formulae may vary from 1 to 5 or more, but is preferably 2 to 3.
- Preferred catalysts from this list are the boron fluoride hydrates [BF3.(HZO)Z] where a: is 1 to 3.
- the quantity of acid produced is limited by the amount of water available and it is hence desirable to use the hydrated strong acid catalyst in sufficient proportion to provide from about one-half to one mole of water per mole of carbon monoxide in the reactor. Additional water may be added during the reaction if desired to maintain the catalyst:water ratio within the preferred range.
- the temperatures employed in the process of this invention may vary from about 50 to 200 C., although preferably from about 60 C. to 150 C.
- the total pressure used in the process of this invention may be as low as about 1 atm., higher pressures give a more favorable reaction rate, and in fact superatmospheric pressures of 1000 atm. or higher may be employed, the upper limit being governed only by the strength of the equipment available. In general, it is preferable to operate within the range of from about 200 atm. to about 1000 atm.
- the process may be operated as a batch, semibatch or continuous process.
- the reactants may be introduced separately as in the example, or they may be premixed in the desired proportions and then charged into the reactor.
- the reactants are maintained in mutual contact by agitation as illustrated in the example, by turbulent flow, or by eflicient bubbling of the gases through the liquid phase or the like.
- Optimum results are usuall obtained when the 4 ethylenic compounds of the invention are injected into a pro-heated mixture of carbon monoxide, water and catalyst.
- 'Ihe carbon monoxide used may be obtained from various commercial sources, e. g., from water gas, producer gas, coke-oven gas or the like. It is preferable, however, to employ reaction ingredients of high purity, with objectionable constituents removed from such commercial gases.
- the beta-halogenopropionic acids having two monovalent hydrocarbon substituents on the alpha carbon and two hydrogens on the beta carbon are useful for various commercial uses. They are especially useful in the preparation of amino acids for pharmaceuticals, foodstuffs, an for polyamide intermediates.
- Process which comprises bringing a reaction mixture containing as essentially the sole oleflnio component. a methallyl halide wherein the halo--, gen is from the 2d to 3d periods of the periodic system under a carbon monoxide pressure of 200 to 1000 atmospheres in contact, at 60-150 C., with a hydrated strong acid catalyst.
- Process which comprises bringing a reaction mixture containing as essentially the sole olefinic component, a methallyl halide under a carbon monoxide pressure of 200 to 1000 atmospheres in contact, at (iii-150 C., with a hydrated strong acid catalyst.
- Process for the preparation of beta-halogenopropionic acids which comprises bringing, as the sole olefinic reactant, an clefinic compound of the formula RCH:C (CH3) CH2 nowadays wherein X is a halogen selected from the 2d and 3d periods of the periodic table and R is selected from the class consisting of hydrogen and alkyls of one to six carbons, under a carbon monoxide pressure of at least 200 atmospheres in contact, at 50-200 C., with a hydrated strong acid catalyst.
- Process for the preparation of beta-halogenopropionic acids having at least one alkyl group and that of not more than six carbons, on the alpha carbon which comprises bringing, as the sole olefinic reactant, an olefinic compound of the formula CHaX wherein X is halogen, R is a monovalent hydrocarbon radical of one to six carbons, and R is selected from the class consisting of hydrogen and monovalent hydrocarbon radicals of one to six carbons in contact at 50-200" C. under a carbon monoxide pressure of at least 200 atmospheres, with a hydrated strong acid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Sept. 14, 1948 PRDCESS FOR THE PREPARATION OF ALPHA, ALPHA DIALKYL BETA-CHLORO- PROPIONIC' ACIDS Thomas Aven'Ford, Wilmington, Del., assigncr to E. I. cliilont de Nemours & Company, Wilmingt'omDeL, a corporation of Delaware No Drawing. Application August 12, 19.46, Serial No. 687,961
7'Claims. I
, This invention relates to. a process. for the proauction of alpha,a1pha-disubstituted-beta-halogenop'ropioni'c acids and, more particularly, of alphaalpha-dirnethyhbeta-chloropropionic acid. In U. S. Patent 1,924,762 a process is disclosed for the preparation of carboxylic acids by reacting an olefin hydrocarbon with carbon. monoxide and steam, desirably with an inorganic acid, over certain catalysts. It is indicated that h" e 3 m 5 with a shaker mechanism was charged to g i g 52M552 ag g ggii g fg ggf gs or its volume with 103.8 parts of boron trifluoride hydro ysis under the reaction conditions. Geri if ('BFTZHZOL, The Vessel was closed! man Patent 568,129 discloses. that vinyl chloride, Connected to source of carbon monoxiqe i reacts with carbon monoxide at elevatedpressure pressured to 500 with this Agltatlon in the presence of aluminum chlorideas catalyst 5 was started and the temperature was raisedto to give a product apparently polymeric. acryly-l chloride. U; Patent 1,993,555. discloses that aliphatic halogenated hydrocarbons react. with steam and carbon monoxidetogive non-halogenated carboxylicv acids having. a. greater number of carbons. in the molecule.
This. invention has as an object the preparation of monomeric halogenated carboxylicacids.
from certainhalosenated olefins. Another object is the preparation of alpha,alpha-disubstituted-beta halogenopropionic acids. Still a further object is to provide-anew one-step process for the preparation of alpha,alpha-dimethylbeta-chloropropionic. acid from relatively cheap raw materials. Qther objects will appear hereinafter.
These objects are accomplished by the following invention wherein carbon monoxide is =reacted under pressure andin. the presence of a 2 bon monoxide in the presence of hydrated boron trifluoride at a temperature within the range of 60 to 150 C. under a pressure of 200 to 1000 atm. The following example, in which parts i are given by weight unless otherwise specified, illus-' hates the invention.
Example I A silver-lined, high-pressure reactor equipped 100 C. with a resultant pressure. rise to 570 atm. With the temperature maintained at 100-102 C. throughout the reaction, methallyl chloride was then injected at about 40 parts per hour over a period of 1.5 hours. The total amount of meth-- allyl chloride. so injected was about 59 parts by weight. By this time, the pressure had reached 750 atm. During the next two hours in which the reaction was continued without further addition of methallyl chloride the pressure dropped to 720 atm. where it remained constant for the next 6.5 hours, indicating that the reaction required at most 3.5 hours, although the totalreaction? time used amounted to approximately ten hours. The reactor was cooled to 25'. C., excess carbon monoxide was bled oil, and the liquid reaction products were discharged, diluted with water and steam distilled. The residue contained a dark oil amounting to 4.5 parts. The
hydrated strong acid catalyst with an organic distillate contained 3 parts of an alkali insoluble ethylenic compoundin which the two remaining 011 and 74 part? of steamfvolame valences of one of the ethylenlc carbons. arerestately 50mm? m Water whlch by 'spectively attached to a ha-logenomethyl group ether uP About 96% of thls W and a mono'valent hydrocarbon radical, the two W 9 rmammg vale-flees 6f the Other ethylemc can a colorless crystalline solid boiling in the range bon atom being satisfied by hydrogen or mdnm of 123-125? {1/30 mm. This fraction had a very valent hydrocarbon radicals sharp freezing point of 44, C. The neutral The ethylemc compounds ractedfby the prom equivalent was found to be 137.0 as compared to ess i v nt f't mul Calculatfid value Of C5H9O2C1 Of 4.5 The process of this inventionis operable only 3 with olefinic compoundswherein the R!- attached gag to the ethylenic carbon bearing the -CH2X X" \Omx group ishydrocarbon since those olefinic com- I pounds having hydrogen on the carbon bearing wherein X is ha1ogen, 'i. e.,. fluorine, chlorine, the CI-12X group do not seem to react in the bromine, or iodine, R. isnydroeen or a mono same way. Thus when the procedure of the vaient hydrocarbon radical, and R is a monoabove example was applied to ally] chloride (in valen't hydrocarbon radical. place of the methallyl chloride), no traceof In a. particularly preferred. practice ofthe inalpha-methyl-beta-ch1oropropionlc acid was vention, metha-llyl chloride is reacted with carfound whether the process was operated at C.
CH2-X wherein X is a halogen, R is hydrogen or a monovalent hydrocarbon radical of 1 to 6 carbon atoms, preferably phenyl or alkyl, and R is a monovalent hydrocarbon radical of 1 to 6 carbon atoms, preferably phenyl or alkyl. Those compounds in which X is chlorine or bromine, i. e., a halogen from the 2d to 3d periods of the periodic system are preferred because these are the most readily available and economical to use. Specific examples include 3-bromo-2-methylpropene, 3-iodo-2-methylpropene, 1-chloro-2- methy1-2-butene, 1-bro-mo-2-methyl-2-butene, 1- bromo-2,6-dimethyl-2-heptene, and l-bromo- 2,3-diphenyl-2-butene.
The molar ratio of the ethylenic compounds of this invention to the carbon monoxide may vary within the range of from 1:1 to 1:20 or more. In general. however, it is preferable to use a large excess of carbon monoxide and molar ratios of 1:5 to 1:10 have been found to be especially desirable.
Strong acid catalysts, in general, are suitable for the operation of this invention although the acid-reacting hydrates, for example, such as BF3.(H20)r, I-I2SO4.(H20) :c, and H3PO4.(I-I20)e and the like are especially desirable. The subscript a: in the foregoing formulae may vary from 1 to 5 or more, but is preferably 2 to 3. Preferred catalysts from this list are the boron fluoride hydrates [BF3.(HZO)Z] where a: is 1 to 3.
The quantity of acid produced is limited by the amount of water available and it is hence desirable to use the hydrated strong acid catalyst in sufficient proportion to provide from about one-half to one mole of water per mole of carbon monoxide in the reactor. Additional water may be added during the reaction if desired to maintain the catalyst:water ratio within the preferred range.
The temperatures employed in the process of this invention may vary from about 50 to 200 C., although preferably from about 60 C. to 150 C.
Although the total pressure used in the process of this invention may be as low as about 1 atm., higher pressures give a more favorable reaction rate, and in fact superatmospheric pressures of 1000 atm. or higher may be employed, the upper limit being governed only by the strength of the equipment available. In general, it is preferable to operate within the range of from about 200 atm. to about 1000 atm.
' The process may be operated as a batch, semibatch or continuous process. The reactants may be introduced separately as in the example, or they may be premixed in the desired proportions and then charged into the reactor. The reactants are maintained in mutual contact by agitation as illustrated in the example, by turbulent flow, or by eflicient bubbling of the gases through the liquid phase or the like. Optimum results are usuall obtained when the 4 ethylenic compounds of the invention are injected into a pro-heated mixture of carbon monoxide, water and catalyst.
'Ihe carbon monoxide used may be obtained from various commercial sources, e. g., from water gas, producer gas, coke-oven gas or the like. It is preferable, however, to employ reaction ingredients of high purity, with objectionable constituents removed from such commercial gases.
The products obtained by the process of this invention, the beta-halogenopropionic acids having two monovalent hydrocarbon substituents on the alpha carbon and two hydrogens on the beta carbon, are useful for various commercial uses. They are especially useful in the preparation of amino acids for pharmaceuticals, foodstuffs, an for polyamide intermediates.
The foregoing detailed description has been given for clearness of understanding only and no unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described for obvious modifications will occur to those skilled in the art.
What is claimed is:
1. Process for the preparation of alpha,alphadimethyl-beta-chloropropionic acid which comprises bringing a reaction mixture containing methallyl chloride as essentially the only olefinic component under a carbon monoxide pressure of 200 to 1000 atmospheres in contact, at 60-150 C., with boron trifluoride dihydrate.
2. Process for the preparation of alpha,alphadimethylbeta-chloropropionic acid which comprises bringing a reaction mixture containing methallyl chloride as essentially the only olefinic component under a carbon monoxide pressure of 200 to 1000 atmospheres in contact, at (SO-150 C., with a hydrated strong acid catalyst.
3. Process which comprises bringing a reaction mixture containing as essentially the sole oleflnic component, a methallyl halide wherein the halogen is from the 2d to 3d periods of the periodic system under a carbon monoxide pressure of 200 to 1000 atmospheres in contact, at (SO- C., with boron trifiuoride dihydrate. I
4. Process which comprises bringing a reaction mixture containing as essentially the sole oleflnio component. a methallyl halide wherein the halo--, gen is from the 2d to 3d periods of the periodic system under a carbon monoxide pressure of 200 to 1000 atmospheres in contact, at 60-150 C., with a hydrated strong acid catalyst.
5. Process which comprises bringing a reaction mixture containing as essentially the sole olefinic component, a methallyl halide under a carbon monoxide pressure of 200 to 1000 atmospheres in contact, at (iii-150 C., with a hydrated strong acid catalyst.
6. Process for the preparation of beta-halogenopropionic acids which comprises bringing, as the sole olefinic reactant, an clefinic compound of the formula RCH:C (CH3) CH2?! wherein X is a halogen selected from the 2d and 3d periods of the periodic table and R is selected from the class consisting of hydrogen and alkyls of one to six carbons, under a carbon monoxide pressure of at least 200 atmospheres in contact, at 50-200 C., with a hydrated strong acid catalyst.
7. Process for the preparation of beta-halogenopropionic acids having at least one alkyl group and that of not more than six carbons, on the alpha carbon which comprises bringing, as the sole olefinic reactant, an olefinic compound of the formula CHaX wherein X is halogen, R is a monovalent hydrocarbon radical of one to six carbons, and R is selected from the class consisting of hydrogen and monovalent hydrocarbon radicals of one to six carbons in contact at 50-200" C. under a carbon monoxide pressure of at least 200 atmospheres, with a hydrated strong acid.
THOMAS AVEN FORD.
. 6 REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,924,765 Larson Aug. 29, 1933 1,924,762 Woodhouse Aug. 29, 1933 2,020,689 Larson Nov 12,- 1935 2,025,677 Woodhouse Dec. 24, 1935 2,033,161 Vail Mar. 10, 1936 2,135,459 Loder Nov. 1, 1938 Loder Oct; 8, 1942 Certificate of Correction Patent No. 2,449,163. September 14,1948 l THOMAS AVEN FORD It is hereby certified that errors appear in the above numbered patent requiring correction as follows:
In the heading to the printed specification, line 8, for Application August 12, 1946 read Application August 2, 1946; column 2, line 44, for value of read value for; column 3, line 75, for usuall read usually; column 5, line 9, claim 7, before monovalent insert saturated;
and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 15th day of March, A. D. 1949.
THOMAS F. MURPHY,
Assistant Uommz'ssz'oner of Patents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US687961A US2449163A (en) | 1946-08-12 | 1946-08-12 | Process for the preparation of alpha, alpha-dialkyl beta-chloropropionic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US687961A US2449163A (en) | 1946-08-12 | 1946-08-12 | Process for the preparation of alpha, alpha-dialkyl beta-chloropropionic acids |
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| Publication Number | Publication Date |
|---|---|
| US2449163A true US2449163A (en) | 1948-09-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US687961A Expired - Lifetime US2449163A (en) | 1946-08-12 | 1946-08-12 | Process for the preparation of alpha, alpha-dialkyl beta-chloropropionic acids |
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| US (1) | US2449163A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166568A (en) * | 1965-01-19 | Therapeutic compositions containing | ||
| US3385888A (en) * | 1965-02-01 | 1968-05-28 | Du Pont | Method for preparing chloropivalic acid |
| US3432548A (en) * | 1965-09-22 | 1969-03-11 | Du Pont | Process for producing alpha,alpha, dimethyl-beta- halopropionic acids |
| USH53H (en) | 1984-02-21 | 1986-04-01 | Fmc Corporation | Processes for producing herbicide intermediates |
| WO2022088306A1 (en) * | 2020-10-28 | 2022-05-05 | 山东兴强化工产业技术研究院有限公司 | Method for preparing intermediate 4,4-dimethylisoxazol-3-one |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1924762A (en) * | 1932-11-11 | 1933-08-29 | Du Pont | Preparation of carboxylic acids |
| US1924765A (en) * | 1931-11-25 | 1933-08-29 | Du Pont | Preparation of carboxylic acids from olefinic hydrocarbons, carbon monoxide, and steam |
| US2020689A (en) * | 1932-10-25 | 1935-11-12 | Du Pont | Process for the preparation of aliphatic carboxylic acids |
| US2025677A (en) * | 1932-10-25 | 1935-12-24 | Du Pont | Process for the preparation of organic acids |
| US2033161A (en) * | 1933-03-25 | 1936-03-10 | Du Pont | Acid synthesis process |
| US2135459A (en) * | 1936-07-07 | 1938-11-01 | Du Pont | Preparation of organic acids from olefines and carbon monoxide |
| US2217650A (en) * | 1937-06-26 | 1940-10-08 | Donald J Loder | Preparation of organic acids |
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1946
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1924765A (en) * | 1931-11-25 | 1933-08-29 | Du Pont | Preparation of carboxylic acids from olefinic hydrocarbons, carbon monoxide, and steam |
| US2020689A (en) * | 1932-10-25 | 1935-11-12 | Du Pont | Process for the preparation of aliphatic carboxylic acids |
| US2025677A (en) * | 1932-10-25 | 1935-12-24 | Du Pont | Process for the preparation of organic acids |
| US1924762A (en) * | 1932-11-11 | 1933-08-29 | Du Pont | Preparation of carboxylic acids |
| US2033161A (en) * | 1933-03-25 | 1936-03-10 | Du Pont | Acid synthesis process |
| US2135459A (en) * | 1936-07-07 | 1938-11-01 | Du Pont | Preparation of organic acids from olefines and carbon monoxide |
| US2217650A (en) * | 1937-06-26 | 1940-10-08 | Donald J Loder | Preparation of organic acids |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166568A (en) * | 1965-01-19 | Therapeutic compositions containing | ||
| US3385888A (en) * | 1965-02-01 | 1968-05-28 | Du Pont | Method for preparing chloropivalic acid |
| US3432548A (en) * | 1965-09-22 | 1969-03-11 | Du Pont | Process for producing alpha,alpha, dimethyl-beta- halopropionic acids |
| USH53H (en) | 1984-02-21 | 1986-04-01 | Fmc Corporation | Processes for producing herbicide intermediates |
| WO2022088306A1 (en) * | 2020-10-28 | 2022-05-05 | 山东兴强化工产业技术研究院有限公司 | Method for preparing intermediate 4,4-dimethylisoxazol-3-one |
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